Nu-acylaminocarboxylic acid-ethylene oxide addition products



Unite s rates atnt Oifice Patented June 28, 1960 N ACYLAMlNOCARBOXYIJIC ACID ETHYLENE OXIDE ADDITION PRODUCTS This invention relates to N:-acylaminocarboxyli c acidethylene oxide addition. products.

N-acylatedaminocarboxylic acids may be prepared by. reacting an aminocarboxylic acid' with a carbonyl chloride, in the presence of an acid bindingmaterial; If the carbonyl chlorides are derived from higher molecular carboxylic acids, particularly those which contain a hydrocarbon radical, having an aliphatic component with 8 to 26, and preferably 10 to 20"carbon atoms, the end acylated aminocarboxylic acids have surface active propcrties and are useful as detergents or detergent components. These N-acylaminocarboxylic acids have the forn'iula:

inwhich R is a hydrocarbon radical containing an aliphatic componentlwith about 8 to 26 carbon atoms and n is a whole number from 3 to '7. These acylaminocarbox'ylic acids may be used-in the form of their watersoluble salts.-

In our co-pending application, Serial No. 677,236 filed August 9, 1957, aprocess is described for the production of N-acylaminocarboxylic acids of the above type, having more than one of the aminocarboxylic acid radicals'. These N-acylaminocarboxylic acids have the general formula:

in which: R is ahydrocarbonradica-l containing an altphatic component with 8 to 26, and: preferably: l to 20 carbon a QInS, S a Wholenurnber-from 3 to 7, and x is a whole number from 2 to 10, and preferably not.

more than 5 and more; preferably not more than 3. These N acylaminocarboxylic acids having more than 1 aminocarboxylic' acid radical, may be produced in accordance with the said application, by reacting a lactam, which contains 3 to 9 atoms in itsheterocyclic ring with a free c irboxylie acid whichcontains at least 8 carbon atoms in its molecule. These N-acylaminocarboxylic acids may be produced in admixture with a major portion of acylaminocarboxylic acids containing but a single amino'carboxylic acid radical and-all of thematerials may be used as detergents or detergent components, inthe form of theirwater-soluble salts. These materials exhibit excellent was-hing properties in soft water but these washing properties are detrimentall'y' effected in hard Water.

One; object of this invention is a surface active deriva tive' ofan N-acylaminocarboxylic acid of the abovementioned' type which is not d'etrimentally effectedby hard water.

This, and still further objects will become apparent from the following' description;

" In accordance with the invention, there has been found that addition products: of salts of the abovementioned acylaminocarboxylic acids with ethylene oxide, exhibit excellent washing" properties and a high resistance to Water hardness. 1

he addit on psor as s. n ac ordance. h the nvention, are addition products-with 1 to 2Q mols of-ethyl'ene oxide of salts of N.-acylaminocarboxylic. acids, having the general formula:

in which R is a hydrocarbon radical containing an aliphatic component with: about 8 to 26 and preferably 10 to 20 carbon atoms, n: is a. whole. number from 3 to 7, x is a. whole. number from. L to: 10, preferably not more than 5', and more. preferably not more than 3, and Me represents the: ion of. amonovalent base.

The. starting acyl'aminocarboxylic. acids may be any of the. known acylamiuocarboxylic. acids, including those describedin co-pending application-677,236i, falling under I K may be. aliphatic on cycloaliphatic in nature and may be connected tot-he carbonyl" group through an aromatic radical. The starting materials, in accordance with the invention, are preferably salts of N-acylaminocarboxylic acids, which are derivedfrom straight chain or branch chain fatty acids of natural or-synthetic origin, including saturated and unsaturated fatty acids of this type. Examples of these fatty acids include caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, palinitic acid, stearic acid, oleic acid, linoleic acid, behenic acid, montan acid and" the like, or any desired mixture of these acids. The salts may also be derived from cycloali'phaticcarboxylic acid such as the resin or naphthene acids, as for example, abietic acid; alkylcyclohexyl carboxylic acids and partially or completely hydrogenated diphenylcarboxylic acids, triphenylcarboxylic acids, benzyl-benzoicacid, benz ylnaphthoic acid and their substitution products, particularlyalkyl derivatives of the said carboxylic acids Additionally, salts derived from alkyl or cycloalkylenbenzoic' acid as well as from carboxylic acids obtained from these aromatic carboxylic acids by partial or complete hydrogenation may be used.

The starting; salts mayalso be derived from other carboxylic acids, the radicals of which bound to the carboxylic group, do not constitute pure hydrocarbon, as for example, ether carboxylic acid, suchas those-derived from glycolie acid. These compounds maybe obtained, for example, by reacting the alcohols with halogen carboxylates, and particularly with chloracetates in the presence ofacid binding agents.

The saltsmay be salts with any bases, including organic or inorganic bases, so that Me represents an ion of a monovalent base. As inorganic cations, there are included lithium, sodium and potassium, while the organic bases include trimethylamine, triethylamine, and similar amines, and preferably those which do not contain any reactive hydrogen atoms,

The reaction of the starting salts of; the N-acylaminocarboxylic acids with the ethylene oxide is effected by heating the two components; in. contact to a temperature of at least C4, preferably, in the; absence of Water. The reaction may be efiected at normal or elevatedhpressures. At normal pressure, it is advisable, to employ somewhat higher temperatures, as for example, temperatures between about 1'50 and 250 C; When Working under pressure, the reaction velocity is sufiicient even at temperatures within; he range of 100; to C. The

ethoxylation is aided by the. presence of materials of a bonates, soaps,,al.9 .Qlates-, etc, The quantity of such, catalysts.- ean.-cO Stitute;0.1- to; 131% by weight and; pref-q erably 0:1 10.12% v-weigh s he. starting m terial If the reaction is eifected in an autoclave, the pressure may be varied between any value, from about 1 atmosphere gauge to the saturation pressure of the ethylene oxide at the reaction temperature used. Advantageously, operation is efifected in such a manner that fresh ethylene oxide is forced into the autoclave, either continuously or batchwise, as a function of the decrease in pressure.

It is advisable to flush the autoclave with an inert gas, as for example, carbon dioxide or nitrogen, before starting the reaction and possibly to pass small quantities of the inert gas under pressure into the autoclave, so that a small pressure, as for example, between about 0.5- atmospheres gauge is obtained prior to the reaction.

The quantity of the ethylene oxide to be added depends on the desired properties of the reaction product. Upon the addition of even 1 mol of ethylene oxide per mol of the N-acylaminocarboxylate, there is obtained a noticeable improvement in the solubility properties, and particularly the resistance to hard water. Of particular technical interest are compounds containing from 3 to mols of ethylene oxide, though larger amounts, as for example, up to about 20 mols of ethylene oxide may be added.

The addition compounds, in accordance with the invention, exhibit low foaming, high resistance to hard water and excellent washing properties. The compounds are particularly suitable as non-foaming white laundering detergents, especially adapted for washing machine use.

When used as detergents for white goods the addition compounds are preferably employed in the form of their water-soluble salts, with inorganic or organic bases, in an aqueous solution, at a concentration of at least 05-15 grams per liter, and preferably 1 to 6 grams per liter. The addition compounds may be combined with all the customary components of washing agents. These include the washing alkalis or neutral salts. As washing alkalis there may be used, in particular, the carbonates or orthophosphates of the alkalis or organic bases, while as neutral salt, sodium sulfate may be mentioned. As further washing-agent components, there enter into question the anhydric phosphates, primarily the pyrophosphates, polyphosphates and metaphosphates. The two latter include, in particular Na P O and (NaPO The washing-agents or components may additionally contain peroxy compounds, and in particular, perborates in order to obtain a bleaching action. The washing effect may further be increased by the addition of known watersoluble colloid substances, such as ether carboxylic acids or ether sulfonic acids of cellulose or starch, cellulose sulfates, alginates, methyl cellulose, glue, gelatins, etc. The detergents containing a novel addition compound, in accordance with the invention, may, for example, have the following composition:

570%, preferably -50% surface-active N-oxyethylated acylaminocaproic acids or their water-soluble salts 0-70%, preferably l050% washing alkalis 0-50%, preferably 0 neutral salts 0-2%, preferably 0.051% colloids 0-40%, preferably 520% other washing agent additives 0-0.5%, preferably 0.01-0.2% optical brighteners The following examples are given by way of illustration and not limitation. In all of the examples, the percentages are percentages by weight:

Example 1 In a stainless steel autoclave provided with an agitator 210 grams of the sodium salt of stearoylaminocaproic acid (0.5 mol) are heated to 120C. under a nitrogen atmosphere of 3 atmospheres and thereupon 176 grams of liquid ethylene oxide (4 mols) are introduced from a storage autoclave by nitrogen pressure in such portions that the pressure increase is not more than 10 atrn. The absorption of the ethylene oxide can be noted from the pressure decrease which occurs. The solid reaction product obtained after cooling can be recrystallized from methyl alcohol.

Example 2 In a stainless steel autoclave provided with an agitator 196 grams of the sodium salt of palmitoylaminocaproic acid (0.5 mol) are heated to l20-130 C. under a nitrogen atmosphere of 3 atmospheres and thereupon reacted with 132 grams (3 mols) of ethylene oxide, which is added in portions from a storage autoclave in accordance with the drop in pressure observed. A practically colorless mass is obtained as reaction product.

Example 3 In a four-neck glass flask of 500 cc. capacity provided with agitator, thermometer, gas inlet and gas outlet tubes, 210 grams of the sodium salt of stearolyaminocaproic acid are heated in a stream of nitrogen up to the melting point, i.e., up to 210 C., whereupon ethylene oxide is introduced into the molten mass until the increase in weight is 88 grams (2 mols ethylene oxide). The cooled solid reaction product can be recrystallized from methyl alcohol for its purification.

Example 4 Detergents of the following composition are prepared in a manner known per se:

Percent by weight Active substance 15 Na5P3010 Na P O 21 N32S04 Cellulose glycolate 0.2

Balance water 26 carbon atoms, n is a whole number from 3 to 7 and'x is a whole number from 1 to 5 and Me is an inorganic cation selected from the group consisting of sodium, potassium, and lithium.

2. Addition compounds, according to claim 1, pontaining from '3 to 10 mols of ethylene oxide. j

3. Addition compound, according to claim 1, n which R is a fatty acid radical containingfrom 10 to 20 carbon atoms.

4. A detergent containing the addition product of 1 to 20 mols of ethylene oxide with a salt of an N-acylaminocarboxylic acid, having the general formula: RCO-[NH-(CH ),,CO] -OMe in which R is a fatty acid radical containing from 8 to 26 carbon atoms, n is a whole number from 3 to 7 and x is a whole number from 1 to 5 and Me is an inorganic cation selected from the group consisting of sodium, potassium and lithium.

5. Method for the'preparation of hard-water resistant surface active derivatives of N-acylaminocarboxylic acid which comprises contacting an N-acylaminocarboxylic acid salt containing a higher fatty acid radical with ethylene oxide at a temperature of at least C., and recovering the addition product formed.

6. Method according to claim 5, in which said N-acylaminocarboxylic acid salt has the general formula:

6 in which R is a fatty acid radical containing from 8 to 26 9. Process according to claim 5, in which said concarbon atoms, n is a whole number between 3 and 7, x tacting is effected in the presence from about 0.1 to 10% is a whole number between 1 and 5 and Me is an inorganic of an alkaline material. cation selected from the group consisting of sodium,

P um, and lithium. 5 References Cited in the file of this patent 7: according to Claim 6, in which Said con- P tactmg is effected at a temperature between about 100 and C. 2,131,142 Orthner et a1. Sept. 27, 1938 8. Process according to claim 7, in which said contacting is effected at an elevated pressure at temperature be- 10 FOREIGN PATENTS tween about 100 and 150 C. 308,747 Switzerland Oct. 1, 1955 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2 943 O99 June 28V 1960 Manfred Dohr et. al.,

It is hereby certified that error appears in the-printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 4L line 17 for "-stearolyaminocaproic" read stearoylaminocaproic -3 line 4L9 before.:"-26 carbon atoms insert in which R is a fatty acid radical containing from 8 to Signed and sealed this 29th day of November 1960.,

( SEA L) Attest:

KARL H. AXLINE ROBERT C. WATSON Attesting Oflicer Commissioner of Patents 

1. THE ADDITION PRODUCT OF 1 TO 20 MOLS OF ETHYLENE OXIDE WITH A SALT OF AN N-ACYLAMINOCARBOXYLIC ACID, HAVING THE GENERAL FORMULA: 